Phosphor, process for producing the same, and luminescent device

ABSTRACT

A green phosphor for emitting light, a spectrum of which is sharp, in an ultraviolet and visible light region, which has higher green light brightness than the conventional rare earth-activated sialon phosphor and has higher durability than the conventional oxide phosphor, is provided. The phosphor being characterized in that Al and a metal element M (here, M is Eu) are incorporated into a crystal of a nitride or oxynitride having a βSi 3 N 4  crystal structure as a solid solution, the content of oxygen in the crystal does not exceed 0.8% by mass, and that the phosphor emits a visible light having a luminescence peak wavelength in the range of 450 nm to 650 nm upon exposure to an excitation source is provided. This luminescence spectrum has a sharp spectrum shape. A manufacturing method of the phosphor, a lighting device and an image display device utilizing the phosphor are also provided.

FIELD OF THE INVENTION

The present invention relates to a phosphor which emits a visible lightupon excitation by an ultraviolet ray, a visible light, or an electronbeam and has a β-type Si₃N₄ crystal structure, wherein the luminescencepeak has a small half-value width and a sharp peak shape, amanufacturing method of the phosphor, and a luminescence deviceutilizing the phosphor.

BACKGROUND ART

The phosphor is utilized in a fluorescent display tube (VFD:vacuum-fluorescent display), a field emission display (FED: FieldEmission Display) or SED (Surface-Conduction Electron-Emitter Display),a plasma display panel (PDP: Plasma Display Panel), a cathode-ray tube(CRT: Cathode-Ray Tube), a white light-emitting diode (LED:Light-Emitting Diode), and so on. In any of these applications, it isnecessary to provide the phosphor with energy to excite the phosphor inorder to have the phosphor emit the fluorescence and the phosphor isexcited by an excitation source with high energy such as a vacuumultraviolet ray, an ultraviolet ray, an electron beam, and a blue lightso as to emit a visible light ray. However, the phosphor is exposed tosuch excitation source that the luminance of the phosphor tends todeteriorate and lower the degree of the brightness. Therefore, thephosphor having little degradation in the brightness is desired.Therefore, a sialon phosphor is proposed as a phosphor having littledegradation in the brightness instead for the conventional phosphor suchas silicate phosphor, phosphate phosphor, aluminate phosphor, sulfidephosphor, and so on.

As an example of this sialon phosphor is manufactured in the followingmanufacturing process as generally described below. First, siliconnitride (Si₃N₄), aluminum nitride (AlN), europium oxide (Eu₂O₃) aremixed with predetermined respective molar ratios and the resultantmixture is fired by a hot press method in one atmospheric pressure (0.1MPa) of nitrogen atmosphere at 1700° C. for one hour (for example, referto Patent reference 1). It is reported that a-sialon activated with Euion manufactured in the above process became a phosphor to emit a yellowlight of wavelength range of 550 nm to 600 nm when it was excited by theblue light having a wavelength range of 450 to 500 nm.

Further, a blue phosphor activated by Ce having a host crystal of JEMphase (LaAl(Si_(6-z)Al_(z))N_(10-z)O_(z)) (refer to Patent reference 2),a blue phosphor activated by Ce having a host crystal of La₃Si₈N₁₁O₄(refer to Patent reference 3), and a red phosphor activated by Eu havinga host crystal of CaAlSiN₃ (refer to Patent reference 4) are known.

As another sialon phosphor, a phosphor of I3-type sialon doped with arare earth element is also known (refer to Patent reference 5) and it isshown that phosphors activated by Tb, Yb, and Ag are those which emit agreen light of 525 nm to 545 nm. However, a phosphor having a highemission intensity has not been obtained since the activation elementsare not well incorporated in the host crystal as a solid solution, butreside in the boundary phase because the synthesis temperature is so lowas 1500° C.

As a sialon phosphor to emit fluorescence of high brightness, β-typesialon phosphor doped with divalent Eu is also known (refer to Patentreference 6) and it is shown that it becomes a green phosphor.

[Patent Document 1] Specification of Japanese Patent No. 3,668,770

[Patent Document 2] WO 2005/019376

[Patent Document 3] Japanese Patent Application Publication No.2005-112922

[Patent Document 4] WO 2005/052087

[Patent Document 5] Japanese Patent Application Publication No.S60-206889

[Patent Document 6] Japanese Patent Application Publication No.2005-255895

In the application of a backlight for a liquid crystal display, onlythree colors: red, green, and blue are necessary, but other colorelements are not necessary. Therefore, only three kinds of phosphorshaving sharp spectra of red, green, and blue are necessary for thisapplication. It is hardly possible to find, in particular, a greenphosphor to emit luminescence which exhibits a sharp peak and high colorpurity. The green phosphor of β-type sialon described in Patentreference 6 exhibits a relatively wide spectrum so that it is hardly tosay the sharpness is enough.

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention

An object of the present invention is to try to satisfy such demand andto provide a green phosphor that emits a green emission spectrum withnarrower width than that of the conventional rare earth activated sialonphosphor and that has higher durability than the conventional oxidephosphor.

Means to Solve the Problem

The present inventor has found that some nitride including Eu, Si, Al,O, and N which has a specific composition range, a specific solidsolution state, and a specific crystal phase becomes a phosphor thatemits a fluorescent light having a fluorescent peak in a wavelengthrange from 520 nm to 550 nm after he devoted himself to theinvestigation in such a circumstance. That is, it has been found that asolid solution crystal being doped with divalent Eu as a luminescencecenter, having a nitride or oxynitride of a β-type Si₃N₄ crystalstructure as the host crystal, having a composition in which oxygencontent does not exceed 0.8 mass % becomes a phosphor that emits afluorescence having a peak in the wavelength range of 520 nm to 550 nmand exhibiting a sharp luminescence spectrum with a half-value width 55nm or less. Further, as a method of manufacturing such phosphor, amethod to synthesize β-type sialon by using metal Si as a source of Siand nitriding the metal Si has been found. Further, a method to reduceoxygen content by heat-treating β-type silicon nitride raw material orβ-type sialon phosphor in a reduction atmosphere has been found.

That is, the important discovery that a phosphor of a specificcomposition among sialon crystals having β-type Si₃N₄ crystal structuredoped with Eu as a solid solution can be used as a phosphor that emits agreen luminescence having a sharp spectrum upon excitation by anultraviolet ray, a visible light, and an electron beam or an X-ray ismade for the first time by the present inventor. The present inventorcontinued to intensively conduct the investigation on the basis of thisdiscovery such that the present inventor has successfully found aphosphor to emit luminescence with a high brightness in a specificwavelength region, a manufacturing method of the phosphor, and alighting device utilizing the phosphor. Details are described morespecifically below.

-   (1) A phosphor comprising: a nitride or oxynitride crystal having a    I3-type Si₃N₄ structure including Al and metal element M (here, M is    Eu) as a solid solution wherein oxygen content contained in the    crystal is 0.8 wt % or less.-   (2) The phosphor according to the above (1) wherein the phosphor    emits luminance having a peak wavelength in a range of 520 nm to 550    nm upon irradiation of an excitation source.-   (3) The phosphor according to the above (1) wherein the phosphor    emits luminance having a peak wavelength in a range of 520 nm to 535    nm upon irradiation of an excitation source.-   (4) The phosphor according to the above (1) wherein the phosphor    emits luminance derived from divalent Eu upon irradiation of an    excitation source and a half-value width of a peak of the luminance    is 55 nm or less.-   (5) A manufacturing method of a phosphor comprising: firing a raw    mixture comprising: at least metal powder including Si; metal or    inorganic compound thereof including Al; metal or inorganic compound    thereof including M (here, M is Eu), in an atmosphere containing    nitrogen in a temperature range of 1200° C. or higher and 2200° C.    or lower.-   (6) The manufacturing method of the phosphor according to the above    (1), wherein the metal or inorganic compound thereof including Al is    aluminum nitride powder, and wherein the metal or inorganic compound    thereof including M is europium oxide powder.-   (7) The manufacturing method of the phosphor according to the above    (1), further comprising: firing the raw mixture powder in the    atmosphere including nitrogen in a temperature range of 1200° C. or    higher and 1550° C. or lower such that nitrogen content of the raw    mixture is increased; and then, firing the raw mixture powder at a    temperature of 2200° C. or less.-   (8) A manufacturing method of a phosphor comprising: an oxygen    content reduction step of reducing oxygen content and increasing    nitrogen content in oxynitride phosphor powder having β-type Si₃N₄    crystal structure including Eu or powder including at least Eu, Si,    Al, O, and N elements by heat-treating the powder in a    reduction-nitridation atmosphere.-   (9) A manufacturing method of a phosphor comprising: heat-treating    silicon nitride raw powder in a reduction-nitridation atmosphere;    adding raw powder containing at least Eu and Al to the treated    powder in which oxygen content is reduced during the heat treatment;    and firing the powder at a temperature of 2200° C. or lower after    the addition.-   (10) The manufacturing method of the phosphor according to the    above (8) or (9) wherein the reduction-nitridation atmosphere    contains ammonia gas, or mixed gas of hydrogen and nitrogen.-   (11) The manufacturing method of the phosphor according to the    above (8) or (9) wherein the reduction-nitridation atmosphere    contains hydrocarbon gas.-   (12) The manufacturing method of the phosphor according to the    above (8) or (9) wherein the reduction-nitridation atmosphere    contains mixed gas of ammonia gas and methane or propane gas.-   (13) A lighting device comprising: a light-emitting diode (LED) or a    laser diode (LD) to emit light of wavelength of 330 to 500 nm and a    phosphor wherein the phosphor comprises a phosphor recited in the    above (1).-   (14) An image display device comprising: at least an excitation    source and a phosphor wherein the phosphor is a phosphor recited in    the above (1).-   (15) The image display device according to the above (14)    comprising: any one of a liquid display panel (LCD), a fluorescent    display tube (VFD), a field emission display (FED), a plasma display    panel (PDP), and a cathode-ray tube (CRT).-   (16) The image display device according to the above (15) wherein    the liquid display panel (LCD) comprises: a LED backlight, wherein    the LED backlight comprises: the phosphor and a light-emitting diode    (LED) to emit light of wavelength of 430 to 480 nm, and wherein the    phosphor further comprises: a red phosphor comprising CaAlSiN₃    activated by Eu.

Effect of the Invention

A phosphor according to the present invention is excellent as a greenphosphor that emits light having a sharp spectrum and narrower peakwidth than that of the prior art sialon phosphor since the phosphorincludes a sialon crystal having β-type Si₃N₄ crystal structure as amain component and the oxygen content contained in the crystal isreduced to 0.8 mass % or lower. Even if the phosphor is exposed to theexcitation source, the brightness of this phosphor is not lowered andnitride compound which leads to a useful phosphor to be utilized in theVFD, FED, PDP, CRT, and, white LED is provided.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereafter, the present invention is described in detail.

The phosphor of this invention comprises a solid solution of a sialonhaving a β-type Si₃N₄ crystal structure (hereafter referred to as“β-type Si₃N₄ group crystal”) as a main component. The β-type Si₃N₄group crystal can be identified by X-ray diffraction or neutron beamdiffraction, and in addition to a substance showing the same diffractionpattern as that of a pure β-type Si₃N₄, a crystal in which latticeconstants have been changed by replacing a constituent element byanother element also belongs to the β-type Si₃N₄ group crystal.Furthermore, point defects, plane defects, or stacking faults may beintroduced into a crystal depending on a solid solution type, and asolid solution element may be condensed in a defective part in aparticle. In that case, however, a crystal whose X-ray diffractionpattern does not change also belongs to the β-type Si₃N₄ group crystal.Further, a polytype having a long-period structure may be formeddepending on periodicity of defect formation. In this case, however, acrystal whose basic structure is the β-type Si₃N₄ crystal structure alsobelongs to the β-type Si₃N₄ group crystal.

Here, the pure β-type Si₃N₄ crystal structure belongs to the hexagonalsystem having P6₃ or P6₃/m symmetry and is a crystal defined as astructure having ideal atom positions. The position of each atomdeviates from the ideal position by ±0.05 angstrom depending on the kindof the atom.

The lattice constants thereof are a=0.7595 nm and c=0.29023 nm. When itsconstituent Si is replaced by an element such as Al, N is replaced by anelement such as O, or a metal atom such as Eu is introduced to form asolid solution, the lattice constants change. However, the basic crystalstructure, sites occupied by the atoms, and atom positions designated bythe coordinates do not change much. Therefore, once the latticeconstants and the plane indices of the pure β-type Si₃N₄ are given, thepositions of X-ray diffraction peaks (2θ) are uniquely determined. Whenthe lattice constants calculated using X-ray diffraction resultsobtained for a new substance coincide with the data from diffractionpeak positions (2θ) calculated using the plane indices of the pureβ-type Si₃N₄, the crystal structure of the new substance is determinedto be identical to that of the pure β-type Si₃N₄.

In the present invention, it is desirable from a viewpoint offluorescence emission that a sialon crystal phase as a constituentcomponent having the β-type Si₃N₄ crystal structure is as pure aspossible and as much as possible. And the sialon crystal phase ispreferably composed of a single phase. But it may also be composed of amixture with other crystalline phases or amorphous phases in a rangewhere phosphor characteristics do not deteriorate. In order to obtainthe high brightness in this case, the content of the sialon crystalphase having the β-type Si₃N₄ crystal structure is preferably 50 mass %or more.

The phosphor has a sialon crystal having β-type Si₃N₄ crystal structureas a host crystal and expresses fluorescence properties by introducing ametal element M (here, M is Eu) into the host crystal as a solidsolution such that M ion serves as a luminescence center to exhibitluminescence characteristics. The β-type sialon crystal containing metalelement Eu as a solid solution in the host crystal emits a greenfluorescence with the high brightness wherein divalent Eu serves as theluminescence center.

In the present invention, by adjusting the oxygen content of the sialoncrystal having the β-type Si₃N₄ crystal structure to 0.8 mass % or lessin a host crystal, a width of an emission peak can be decreased so as tosharpen the peak. A luminescence center ion such as Eu is surrounded byoxygen and nitrogen ions. Since the bonding state changes as Eu isbonded with the oxygen ion or the nitrogen ion, the emission wavelengthsfor the bonds with the oxygen and nitrogen ions are different.Accordingly, if the content of oxygen increases, it is considered thatthe width of the emission peak is increased. It is ideally preferablethat the oxygen content is as low as possible since the peak width canbe small. And this effect to make the peak width small is significant byadjusting the oxygen content to 0.8 mass % or less.

The phosphor to which Eu is added according to the present inventionemits, upon irradiation of an excitation source, a green light which isderived from divalent Eu in a wavelength range of 520 nm to 550 nm andemits fluorescence of a sharp spectrum shape having a half-value widthof 55 nm or less. In particular, the phosphor in which the oxygencontent is decreased to 0.5 mass % or less emits a green light having agood color purity to form an emission spectrum with a peak at anemission wavelength in the range of 520 nm to 535 nm. Moreover, thegreen light has (x, y) values satisfying 0≦x≦0.3 and 0.5≦y≦0.83 on theCIE chromaticity coordinates so as to show the light is green and has agood color purity.

Fluorescent light with a high intensity may be emitted from the phosphorupon irradiation of light as an excitation source having the wavelengththat is at least 100 nm and that does not exceed 500 nm (a vacuumultraviolet ray, a deep ultraviolet ray, an ultraviolet ray, a nearultraviolet ray, a visible light from violet to blue regions) and anelectron beam, an X-ray, and the like.

In particular, the shape of the phosphor according to the presentinvention is not limited to, but it is preferable that the phosphor iscomposed of a single crystal having the average particle size of 50 nmor larger and 20 μm or smaller if the phosphor is used in a powderstate. Further, it is preferable that the average aspect ratio (a valueto be given by dividing length of particle along the major axis bylength of the particle along the minor axis) is equal to or less than1.5 such that the particle is closer to the sphere since it is easy tohandle the phosphor in the process of dispersion and application.

Here, in this specification, the mean particle diameter is defined asfollows. In the measurement by the sedimentation method, the particlediameter is defined as a diameter of an equivalent sphere having thesame sedimentation rate, and in the laser scattering method, it isdefined as a diameter of an equivalent sphere having the same scatteringcharacteristics. Further, the distribution of particle diameters iscalled a particle size (particle diameter) distribution. In the particlediameter distribution, a specified particle diameter is defined as amean particle diameter D50 when the total mass of powder particleshaving diameters larger than the specified particle diameter is 50% ofthe total mass of the entire powder body. These definition and term arewell known to the one skilled in the art and are described in variousdocuments such as JIS Z 8901 “Powder Body for Test and Particle forTest” and the first chapter of “Basic Physical Properties of Powder”edited by The Society of Powder Technology, Japan (ISBN4-526-05544-1).In the present invention, a specimen was dispersed in water in whichsodium hexamethaphosphate was added as a dispersing agent. Then, thevolume-converted integrated frequency distribution of the particlediameters was measured by using a laser scattering-type measurementinstrument. Here, the volume-converted distribution is identical to theweight-converted distribution. The particle diameter corresponding tothat at 50% in the integrated (cumulative) frequency distribution wasobtained and defined as the mean particle diameter D50. It should benoted that, in the following part of this specification, the meanparticle diameter is based on the median value (D50) of the particlesize distribution measured with a particle size distribution measurementmeans by the above-mentioned laser scattering method. As to a means fordetermining the mean particle diameter, various kinds of means have beendeveloped and the development is still being performed such that thevalue measured by a newly developed means may differ slightly. However,it should be understood that the meaning and significance of the meanparticle diameter itself is definite, and the means for measuring themean particle diameter is not necessarily limited to the above-mentionedmeans.

The method for producing the phosphor of the present invention is, inparticular, not limited to, but the following method may be described asan example.

When a raw material mixture comprising at least metal powder containingSi, metal or inorganic compound containing Al, and metal or inorganiccompound containing metal element M (here, M is Eu) is fired in atemperature range of 1200° C. or higher and 2200° C. or lower in anitrogen-containing atmosphere, a phosphor in which M is incorporated asa solid solution into a sialon crystal having the β-type Si₃N₄ crystalstructure can be synthesized.

As a Si source of the raw material mixture, metal powder containing atleast Si is used. As the metal powder containing Si, in addition tometallic Si, a Si alloy including another metal may be cited. As the Sisource, an inorganic substance, such as silicon nitride or sialonpowder, can be simultaneously added in addition to the metal powder. Ifthe silicon nitride or sialon powder is added, the crystallinity of aproduct is improved although the oxygen content increases, and thereforethe brightness of the phosphor is improved. As an Al source of the rawmaterial mixture, a metal or inorganic compound containing Al is used.Metal Al, Al alloy, or aluminum nitride may be cited as an example. As asource of supplying the element M of the raw material mixture (here, Mis Eu), metal M, or an alloy, nitride, oxide, or carbonate containing Mmay be cited. In order to decrease the oxygen content as low aspossible, metal M or nitride of M is desirably used. Nevertheless, theoxide of M may be favorably used in a viewpoint of the industry becausethe raw material is readily available.

As the raw material mixture for synthesizing the phosphor containing Eu,a mixture of metal Si powder, aluminum nitride powder, and europiumoxide powder may be cited. By using the raw material mixture of thesepowders, it is possible to synthesize such phosphor having aparticularly low oxygen content.

The phosphor is synthesized by firing the raw material mixture in thenitrogen-containing atmosphere in a temperature range of 1200° C. orhigher and 2200° C. or lower. The nitrogen-containing atmosphere isnitrogen gas, or a gas of molecule containing a nitrogen atom, and maybe mixed with another kind of gas if necessary. For example, N₂ gas,N₂—H₂ gas mixture, NH₃ gas, and NH₃—CH₄ gas mixture may be cited. Ifheated under these atmospheres, the metal Si in the raw material isnitrided to form Si₃N₄, and then this Si₃N₄ is reacted with anAl-containing raw material and a M-containing raw material such that thephosphor including the sialon crystal having the β-type Si₃N₄ crystalstructure in which M is incorporated as a solid solution is produced. Inthis production process, the phosphor having a low oxygen content may besynthesized since the content of oxygen in the metal Si (normally 0.5mass % or less) is lower than the content of oxygen in Si₃N₄ rawmaterial powder (normally 1 mass % or more). Here, it is preferable thatthe nitrogen-containing atmosphere is an atmosphere that includessubstantially no oxygen, that is, the atmosphere is nonoxidizing.

A nitriding reaction of Si in the raw material powder mixture proceedsat a temperature of 1200° C. or higher and 1550° C. or lower. Therefore,it is possible to employ a technique to synthesize the phosphorcomprising the steps of: firing the raw material powder mixture in thistemperature range such that the nitrogen content in the raw materialpowder mixture is increased to convert Si into Si₃N₄; and firing theresultant product at a temperature of 2200° C. or lower.

As another synthesis method, it is possible to employ another techniqueto synthesize the phosphor comprising the steps of: heat-treatingprecursor raw material mixture powder containing at least Eu, Si, Al, O,and N elements or silicon nitride raw material powder in areduction-nitridation atmosphere such that the oxygen content is loweredas the nitrogen content is increased in the treated powder, therebydecreasing the content of oxygen in the starting material; and firingthe resultant mixture, to which a raw material including Eu or Al isadded if necessary, at a temperature of 2200° C. or lower.

The reduction-nitridation atmosphere is composed of gas which hasreduction ability and nitriding nature, such as ammonia gas, hydrogenand nitrogen gas mixture, ammonia-hydrocarbon gas mixture, andhydrogen-nitrogen-hydrocarbon gas mixture. Moreover, as a hydrocarbongas, methane gas or propane gas is preferable because of the strongreduction ability. Furthermore, it is also possible to heat-treat, in agas having the nitriding nature, a mixture material of the siliconnitride powder and the precursor raw material mixture powder to which,as a carbon source, solid material containing carbon such as carbonpowder and liquid material containing carbon such as phenolic resin areadded in advance.

In still another method, oxynitride phosphor powder having the β-typeSi₃N₄ crystal structure and being doped with Eu may be heat-treated in areduction-nitridation atmosphere so as to decrease the oxygen contentand simultaneously increase the nitrogen content in the treated powder.In this method, a sialon phosphor synthesized by an ordinary method maybe reduced and nitrided to decrease effectively the content of oxygenresiding on the surface of the sialon phosphor.

In this method, the reduction-nitridation atmosphere is also the gashaving the reduction ability and the nitriding nature. For example,ammonia gas, hydrogen and nitrogen gas mixture, ammonia-hydrocarbon gasmixture, or hydrogen-nitrogen-hydrocarbon gas mixture may be cited.Moreover, as the hydrocarbon gas, methane or propane gas is preferablebecause of the strong reducing ability.

In the step of synthesizing the phosphor, particularly high brightnesscan be obtained according to a method of firing a metal compound in apowder or aggregate state which is filled in a container as the packingfraction is maintained to keep the bulk density of the metal compound40% or less. When using fine powder having a particle diameter ofseveral micrometers as the starting material, the mixture of the metalcompound after completion of the mixing step is in an aggregated form(hereafter referred to as a “powder aggregate”) of several hundredsmicrometers to several millimeters, which is constituted of the finepowder having the particle diameter of several micrometers. In thepresent invention, the powder aggregate is fired in a state where thepacking fraction of the powder aggregate is maintained so as to keep thebulk density 40% or less.

More specifically, in an ordinary sialon production, powder is fired bythe hot pressing method or the power is first molded in a die and thenfired. Therefore, the powder is fired in a state of a high packingfraction. In the present invention, however, no mechanical force or noin-advance molding using a mold or the like is applied, and a mixturepowder aggregate whose particle size is uniformized is filled, as it is,in the container or the like by maintaining the packing fraction so asto keep the bulk density 40% or less. If necessary, the particle sizemay be controlled by granulating the powder aggregate to a mean particlediameter of 500 μm or smaller using a sieve, air classification or thelike. Alternatively, the powder aggregate may be directly granulatedinto a size of 500 _(l)am or smaller using a spray dryer or the like.Furthermore, the container made of boron nitride is advantageous becauseboron nitride hardly reacts with the phosphor.

The reason why the firing is performed while the bulk density is kept40% or less is to fire the raw material powder in the state of keeping afree space around the raw material powder. The optimal bulk densitydepends on the shape or surface state of granular particles, and it ispreferably 20% or less. In this state, a reaction product can grow as acrystal growth in the free space such that it is less likely for thegrowing crystals to contact with each other. It is plausible that thecrystals having fewer surface defects can be synthesized as a result.Thus, the phosphor having high brightness is obtained. If the bulkdensity exceeds 40%, partial densification may occur during the firing,resulting in a dense sintered compact which hinder the crystal growthsuch that the brightness of the phosphor may be decreased. Moreover,fine powder material is hardly to be obtained. Further, it isparticularly preferable to adjust the size of the powder aggregate to500 μm or smaller to obtain excellent milling properties after firing.

As described above, the powder aggregate having the packing fraction of40% or less is fired under the abovementioned conditions. A furnace of ametal resistance heating type or graphite resistance heating type ispreferable for the firing because the firing temperature is high and thefiring atmosphere is nitrogen. Further, an electric furnace using carbonas material for hot parts of the furnace is suitable. As a method offiring, a sintering method which does not need application of mechanicalpressurization from the outside, such as a pressureless sinteringprocess and a gas-pressure sintering process, is preferable to performthe firing while the bulk density is kept in a predetermined range.

In the step of synthesizing the phosphor, the nitrogen atmospherepreferably has a pressure in the range of 0.1 MPa or higher and 100 MPaor lower. The pressure is more preferably in the range of 0.1 MPa orhigher and 1 MPa or lower. If the nitrogen gas atmosphere has a pressurelower than 0.1 MPa when silicon nitride is used as the raw material andheated at a temperature of 1820° C. or higher, the raw material iseasily decomposed by heat, which is not so preferable. If the pressureis higher than 0.5 MPa, the decomposition is significantly suppressed. Apressure of 1 MPa is sufficient for this purpose. A pressure of 100 MPaor higher is not suitable for industrial production because a specialfacilities are required.

When the powder aggregate obtained from firing is tightly sintered, thepowder aggregate is ground with a milling machine usually used inindustry, for example a ball mill and a jet mill. In particular, thecontrol of the particle diameter is easy in ball mill. Balls and a potused on this occasion are preferably made of a silicon nitride sinteredcompact or sialon sintered compact. The balls and the pot made of aceramic sintered compact having the same composition as that of thephosphor to be produced is particularly preferable. Milling is applieduntil a mean particle diameter of 5 μm or smaller is obtained. Inparticular, the mean particle diameter is preferably 20 nm or larger and5 μm or smaller. If the mean particle diameter exceeds 5 μm, thefluidity of the powder and the dispersibility of the powder into a resindeteriorate. Consequently, when forming a light emitting unit incombination with a light emitting device, emission intensity becomesnonuniform depending on a portion of the unit. If the mean particlediameter becomes smaller than 20 nm, the powder becomes poor inhandling. When a target particle diameter is not obtained only bymilling, classification can be combined. As a method of classification,a sieving process, air classification process, precipitation process ina liquid or the like may be employed.

As a part of the method of milling and classification, an acid treatmentmay be applied. In most powder aggregates obtained by firing, thenitride or oxynitride single crystals having the β-type Si₃N₄ crystalstructure are tightly aggregated by a small amount of grain boundaryphase including a glass phase as a main component. When the powderaggregate is immersed in an acid having a specific composition, thegrain boundary phase including the glass phase as the main componentselectively dissolves, and the single crystals separate. In this way,individual particles may be obtained as one nitride or oxynitride singlecrystal having the β-type Si₃N₄ crystal structure, but not as aggregateof single crystals. Since such a particle comprises a single crystalhaving fewer surface defects, the brightness of the phosphor isparticularly increased.

Although the fine phosphor powder is obtained according to theabove-mentioned steps, heat treatment is effective in order to furtherimprove the brightness. In this case, the powder after the firing orafter the particle size adjustment by milling or classification can bethermally treated at a temperature of 1000° C. or higher and the firingtemperature or lower. In the case of the thermal treatment at thetemperature lower than 1000° C., the effect of eliminating the defectson the surface is low. In the case of the thermal treatment at thetemperature higher than the firing temperature, milled powder particlesmay be bonded again with each other, which is not so preferable.Although the atmosphere suitable for the heat treatment depends on thephosphor composition, a mixed atmosphere composed of one or two or morekinds of gases selected from nitrogen, air, ammonia, and hydrogen may beused. Since the nitrogen atmosphere is highly effective in eliminatingthe defects, it is preferable.

The nitride to be obtained as described above according to the presentinvention is capable of having a wider excitation range from anultraviolet ray to a visible light as compared with an ordinary oxidephosphor or an existing sialon phosphor. Moreover, the nitride can emitthe visible light, and in particular, the nitride to which Eu is addedcan emit the green light. Further, the nitride is characterized by anarrow emission spectrum width such that it is suitable for a backlightof an image display device. In addition, the nitride does notdeteriorate even when exposed to a high temperature such that it isexcellent in the thermal durability. The nitride is also excellent inthe stability in an oxidizing atmosphere and a humid environment for along period of time.

In the following, the present invention will be described in more detailusing Examples as shown below. These examples, however, are disclosed asthe help for understanding the present invention with ease, and thepresent invention shall not be limited to these Examples.

EXAMPLE Examples 1 to 4

As powdery raw materials, Si powder which had 99.99% purity and waspassed through a 45 μm-sieve (Kojundo Chemical Laboratory Co., Ltd.,reagent grade), aluminum nitride powder having a specific surface areaof 3.3 m²/g and an oxygen content of 0.79% (Tokuyama Corp. F grade), andeuropium oxide powder of 99.9% purity (Shin-Etsu Chemical Co., Ltd.)were used.

Table 1 summarizes design compositions of Examples 1 to 4 andComparative example. Table 2 summarizes the weights of individualcomponents of Examples 1 to 4 and Comparative example which are weighedin order to obtain the respective design compositions in Table 1. Toobtain compounds having the design compositions shown in Table 1(Examples 1 to 4), predetermined amounts of powdery raw materials wereweighed in a proportion of compositions in Table 2, mixed using a mortarand a pestle which were made of a silicon nitride sintered compact for10 minutes or more, and then passed through a 250-μm sieve to obtain apowder aggregate having high fluidity. This powder aggregate was allowedto naturally fall into a crucible made of boron nitride having adiameter of 20 mm and a height of 20 mm. Next, the crucible was set in agraphite resistance heating-type electric furnace. Firing operations aredescribed as follows. First, a firing atmosphere was evacuated with adiffusion pump, and heated from the room temperature to 800° C. at arate of 500° C./h. Nitrogen gas having a purity of 99.999 vol % wasintroduced at 800° C. to set gas pressure to 0.5 MPa, and thetemperature was raised to 1300° C. at a rate of 500° C./h, and thencontinuously raised to 1600° C. at a rat of 1° C./m, and maintained atthe temperature for 8 hours. The synthesized sample was ground to powderusing an agate mortar, and the powder X-ray diffraction measurement(XRD) using the Cu Ka line was conducted for the sample. As a result,all obtained charts showed existence of the β-type silicon nitridestructure.

Next, the heat treatment was again applied to these powders. The powderfired at 1600° C. was ground using a mortar and a pestle which were madeof silicon nitride, and then allowed to naturally fall into a cruciblemade of boron nitride having a diameter of 20 mm and a height of 20 mm.Next, the crucible was set in a graphite resistance heating-typeelectric furnace. Firing operations are described as follows. First, afiring atmosphere was evacuated with a diffusion pump, the furnace washeated from the room temperature to 800° C. at a rate of 500° C/h,nitrogen gas having a purity of 99.999 vol. was introduced at 800° C. toset gas pressure to 1 MPa, the temperature was continuously raised to1900° C. at a rate of 500° C./h, and maintained at the temperature for 8hours. The thus synthesized sample was ground to powder using an agatemortar, and the powder X-ray diffraction measurement (XRD) using the CuKa line was conducted for the sample. As a result, all obtained chartsshowed the existence of the β-type silicon nitride structure. Thecontents of oxygen and nitrogen in these synthetic powders were measuredwith an oxygen/nitrogen analyzer using a combustion process. Themeasurement results of Examples 1 to 4 and Comparative example aresummarized in Table 3. As shown in Table 3, the oxygen contents in thesynthetic powders of Examples 1 to 4 are 0.5 mass % or less.

Here, the oxygen contents shown in Table 3 are higher than those of thedesign compositions (if the oxygen contents are as expected from thedesign compositions in Table 1, the contents are to be 0.11 wt. %). Thereason is considered as follows. The surfaces of silicon powder andaluminum nitride powder used as the starting materials might have beenoxidized to form a silicon oxide film and an aluminum oxide film.Furthermore, when the raw materials were ground through the milling stepand the drying step, the surfaces might have been oxidized so as to makethe oxygen contents larger. Moreover, approximately 1 ppm of oxygen ormoisture was also contained in the nitrogen gas atmosphere for firing ata high temperature, and this oxygen or moisture might have reacted withthe samples, thereby making the oxygen contents higher. For thesereasons, the oxygen contents shown in Table 3 are higher than those ofthe design compositions.

By irradiating the re-heat-treated powder samples with a lamp whichemits light having a wavelength of 365 nm, it was confirmed that each ofthe powder samples emitted a green light. The emission spectra andexcitation spectra of the powder samples were measured using aspectrophotofluorometer. Table 4 summarizes the results of Examples 1 to4 and Comparative example. As shown in Table 4, the powder samples ofExamples 1 to 4 were proved to be green phosphors having excitationspectrum peaks in the wavelength range of 300 nm to 303 nm and peaks inthe wavelength range of 524 nm to 527 nm in the emission spectra. Thesesamples have shorter peak wavelength values than those of greenphosphors having β-type sialon as a host having been reported in thepast and their emission spectra have a good color purity.

FIGS. 1 to 4 show the spectra of the re-heat-treated products of theexamples. The phosphors are characterized by emitting sharp green lightshaving half-value widths of 55 nm or smaller. Since the emissionintensity (counted values) changes depending on measuring instruments orconditions, the indicated unit is an arbitrary unit. In the drawings,the emission intensity of the peak observed in the range of 524 nm to527 nm is normalized to 1.

Next, luminescence characteristics of Example 1 (cathodoluminescence,CL) obtained upon electron beam irradiation were observed using ascanning electron microscope (SEM) equipped with a CL detector, and CLimages were evaluated. This apparatus shows clearly the wavelength oflight emitted at any place by detecting visible light generated by theelectron beam irradiation and obtaining the visible light as aphotographic image being two-dimensional information. FIG. 5 shows theCL spectrum of Example 1 at an accelerating voltage of 5 kV. It isconfirmed by emission spectrum observations that this phosphor wasexcited by the electron beam to emit a green light having a peak at 533nm. The half-value width was 54 nm. Thus, the phosphor of the presentinvention has the peak in the wavelength range of 520 nm to 535 nm and agood color purity upon the electron beam irradiation, and thus it issuitable for the electron beam-excited image display device such as FED.

TABLE 1 Designed Composition (Atomic ratio) Eu Si Al O N Example 10.0050 11.980 0.020 0.010 15.990 Example 2 0.0150 11.940 0.060 0.03015.970 Example 3 0.0275 11.890 0.110 0.055 15.945 Example 4 0.035011.860 0.140 0.070 15.930 Comparative 1 0.0270 12.150 0.490 0.040 15.320

TABLE 2 Mixture Composition (mass %) Si3N4 Si AlN Eu2O3 Example 1 95.1994.545 0.257 Example 2 94.479 4.755 0.766 Example 3 93.590 5.016 1.393Example 4 93.064 5.170 1.766 Comparative 1 95.820 3.370 0.810

TABLE 3 Contents of Oxygen and Nitrogen (mass %) N O Example 1 38.8 0.32Example 2 39.0 0.33 Example 3 39.1 0.40 Example 4 38.9 0.42 Comparative1 38.7 1.12

TABLE 4 Excitation Emission Half-value Wavelength Wavelength Width nm nmnm Example 1 300 524 44 Example 2 301 525 47 Example 3 303 527 52Example 4 302 527 52 Comparative 1 302 527 58

Comparative Example Comparative example 1

In order to obtain a compound having a design composition represented byEu_(0.027)Si_(12.15)Al_(0.49)O_(0.04)N_(15.32), the same powderymaterials as use except Si powder, which was replaced by silicon nitridepowder having an oxygen content of 0.93 wt % and an a-type content of92% (Ube Industries, Ltd., SN-E10 grade). Predetermined amounts ofsilicon nitride powder, aluminum nitride powder and europium oxidepowder were weighed in a proportion of 95.82 mass %, 3.37 mass % and0.81 mass %, respectively, and mixed by using a mortar and a pestlewhich were made of a silicon nitride sintered compact for 10 minutes ormore, and then passed through a 250-μm sieve, thereby obtaining a powderaggregate having high fluidity. This powder aggregate was allowed tonaturally fall into a crucible made of boron nitride having a diameterof 20 mm and a height of 20 mm. Next, the crucible was set in a graphiteresistance heating-type electric furnace, and then the firing atmospherewas evacuated with the diffusion pump and heated from the roomtemperature to 800° C. at a rate of 500° C./h. Nitrogen gas having apurity of 99.999 vol % was introduced at 800° C. to set gas pressure to1 MPa, and the temperature was raised to 1900° C. at a rate of 500° C./hand maintained at the temperature for 8 hours. The synthesized samplewas ground to powder using an agate mortar, and the powder X-raydiffraction measurement (XRD) using the Cu Ka line was conducted. As aresult, all charts obtained showed the existence of the β-type siliconnitride structure. When the contents of oxygen and nitrogen in thesesynthetic powders were measured with an oxygen/nitrogen analyzer using acombustion process, as shown in Table 3, the oxygen content was 1.12mass % and proved to be higher as compared with Example 1 in which themetal silicon was used as the starting material. The oxygen content ofthe silicon nitride powder is higher than the oxygen content of themetal silicon (in which the oxygen content in the raw material is 0.5wt. % or less). Consequently, when the silicon nitride is used as thestarting material, the oxygen content was proved to increase as comparedwith the powder in which the metal silicon powder was used as thestarting material. As shown in FIG. 6, the fluorescence spectrum of thismaterial has a longer emission wavelength of 537 nm and a widerhalf-value width of 58 nm, as compared with the material in which themetal silicon was used as the starting material.

Next, a lighting device using the phosphor comprising the nitride of thepresent invention will be described. FIG. 7 is a schematic structuralconfiguration of a white LED as the lighting device. A phosphor mixture1 containing the nitride phosphor according to the present invention andother phosphors, and a 380 nm near-ultraviolet LED chip 2 as a lightemitting device are used. A coating of the phosphor mixture 1 preparedby dispersing the green phosphor according to Example 1 of the presentinvention, a red phosphor (Y(PV)O₄: Eu) and a blue phosphor(BaMgAl₁₀O₁₇: Eu²⁺ (BAM)) into a resin layer 6 is put on the LED chip 2,and arranged in a container 7. When electric currents flow throughconductive terminals 3 and 4, the electric currents are supplied to theLED chip 2 via a wire bond 5. The LED chip 2 then emits light of 380 nm,which excites the phosphor mixture 1 of the green phosphor, red phosphorand blue phosphor to emit a green light, a red light, and a blue light.The green light, the red light, and the blue light are mixed to yield anilluminating device emitting a white light. This lighting device ischaracterized by high emission efficiency.

Next, an example of designing an image display device using the nitridephosphor of this invention will be described. FIG. 8 shows a schematicdiagram showing a principle of a plasma display panel as an imagedisplay device. A red phosphor (Y(PV)O₄: Eu) 8, the green phosphor 9 ofExample 1 according to the present invention and a blue phosphor(BaMgAl₁₀O₁₇: Eu²⁻ (BAM)) 10 are applied to the internal surfaces ofrespective cells 11, 12 and 13. When electric currents are supplied toelectrodes 14, 15, 16, and 17, vacuum ultraviolet radiation is generatedby Xe discharge in the cells, and the phosphors are excited by thisradiation to emit red, green and blue visible lights. The emitted lightsare observed from the outside via a protection layer 20, a dielectriclayer 19, and a glass substrate 22, so as to work as the image display.

FIG. 9 is a schematic diagram showing a principle of a field emissiondisplay panel as an image display device. The green phosphor 56 ofExample 1 according to the present invention is applied to the internalsurface of an anode 53. By applying the voltage between a cathode 52 anda gate 54, electrons 57 are emitted from an emitter 55. The electronsare accelerated by the voltage between the anode 53 and the cathode andimpinge on the phosphor 56 to excite the phosphor to emit light. Theentire structure is protected by glass 51. The drawing shows a singlelight emission cell comprising one emitter and one phosphor. However, anactual display emitting a variety of colors is built by arranging alarge number of blue and red cells besides green cells. Although thephosphors used for the green and red cells are not particularlyspecified, phosphors which show high brightness under low-voltageelectron beams are preferable.

FIG. 10 is a schematic diagram showing a principle of a liquid crystaldisplay panel as an image display device. The liquid crystal displaypanel comprises: a polarizing filter 71, a light shutter part includingtransparent electrodes 73 to 77 and a liquid crystal (liquid crystalmolecular layer) 78, and backlight sources 70. A white LED having thestructure shown in FIG. 7 is used as a backlight source 70. In FIG. 7, aphosphor mixture 1 containing the nitride phosphor according to thepresent invention and other phosphors, and a 450 nm blue LED chip 2 as alight emitting device are used. A coating of the phosphor mixture 1prepared by dispersing the green phosphor according to Example 1according to the present invention and a red phosphor (CaAlSiN₃: Eu)into a resin layer 6 is put on an LED chip 2, and arranged in acontainer 7. When electric currents flow through conductive terminals 3and 4, the electric currents are supplied to the LED chip 2 via a wirebond 5. The LED chip then emits light of 450 nm, which excites thephosphor mixture 1 comprising: the green phosphor and the red phosphorto emit green and red lights, respectively. The light emitted by thephosphors and the blue light emitted by the LED are mixed to yield awhite light. In FIG. 10, this LED chip is used as a LED backlight 70 fora backlight source. A mixture of red, green and blue lights emitted bythe LED backlight 70 passes through a polarizing filter 71, a glasssubstrate 72 and a transparent electrode 73 to reach a liquid crystalmolecular layer 78. The directions of liquid crystal molecules which arepresent in the liquid crystal molecular layer 78 are changed by thevoltage applied between the transparent electrode 73 serving as a commonelectrode and transparent electrodes 75, 76 and 77 arranged on a pixelelectrode 74 for displaying respective red, green and blue colors, andthis change of molecular directions causes change in light transmission.Light beams having passed through the transparent electrodes 75, 76, and77 further pass through red, green and blue color filters 79, 80, and81, and are emitted outside through the glass substrate 72 and thepolarizing filter 71. In this way, an image is displayed.

This backlight source 70 has a spectrum which comprises sharp blue,green and red light components and is hence excellently separated intothe components by the polarizing filter 71. Therefore, red, green andblue chromaticity points of the spectrally separated light componentshave improved color purity on chromaticity coordinates. In this way, acolor space reproducible by the liquid crystal display is made wider,and a liquid crystal panel having satisfactory color reproducibility canbe provided.

INDUSTRIAL APPLICABILITY

The phosphor of the present invention is excellent as a green phosphorto emit a sharp light having a narrower peak-width if compared to thatof the prior art sialon. Further, the phosphor shows only smalldeterioration of phosphor brightness when exposed to an excitationsource. Hence, the phosphor is used suitably for VFD, FED, PDP, CRT,white LED, and the like. In the future, it is expected that the phosphorwill be extensively utilized in performing the material design ofvarious kinds of display devices such that it may contribute to thedevelopment of the industry.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an excitation spectrum and an emission spectrum byfluorescence measurement of Example 1.

FIG. 2 shows an excitation spectrum and an emission spectrum byfluorescence measurement of Example 2.

FIG. 3 shows an excitation spectrum and an emission spectrum byfluorescence measurement of Example 3.

FIG. 4 shows an excitation spectrum and an emission spectrum byfluorescence measurement of Example 4.

FIG. 5 shows an emission spectrum of Example 1 by CL emission.

FIG. 6 shows an excitation spectrum and an emission spectrum byfluorescence measurement of Comparative example 1.

FIG. 7 is a schematic diagram showing a lighting device (LED lightingdevice) according to the present invention.

FIG. 8 is a schematic diagram showing an image display device (Plasmadisplay panel) according to the present invention.

FIG. 9 is a schematic diagram showing an image display device (FieldEmission Display) according to the present invention.

FIG. 10 is a schematic diagram showing an image display device (liquidcrystal display panel) according to the present invention.

DESCRIPTION OF NUMERICAL REFERENCES

-   1 mixture of red phosphor, blue phosphor, and green phosphor    (Example 1) according to the present invention-   2 LED chip-   3, 4 conductive terminal-   5 wire bond-   6 resin layer-   7 container-   8 red phosphor-   9 green phosphor-   10 blue phosphor-   11, 12, 13 ultraviolet-emitting cell-   14, 15, 16, 17 electrodes-   18, 19 dielectric layer-   20 protection layer-   21, 22 glass substrate-   51 glass-   52 cathode-   53 anode-   54 gate-   55 emitter-   56 phosphor-   57 electron-   70 LED backlight (backlight source)-   71 polarizing filter-   72 glass substrate-   73 transparent electrode (common electrode)-   74 transparent electrode (pixel electrode)-   75 transparent electrode (for displaying red)-   76 transparent electrode (for displaying green)-   77 transparent electrode (for displaying blue)-   78 liquid crystal molecular layer-   79 color filters (for displaying red)-   80 color filters (for displaying green)-   81 color filters (for displaying blue)

1. A phosphor comprising: a nitride or oxynitride crystal having aβ-type Si₃N₄ structure including Al and metal element M (here, M is Eu)as a solid solution wherein oxygen content contained in the crystal is0.8 wt % or less.
 2. The phosphor according to claim 1 wherein thephosphor emits luminance having a peak wavelength in a range of 520 nmto 550 nm upon irradiation of an excitation source.
 3. The phosphoraccording to claim 1 wherein the phosphor emits luminance having a peakwavelength in a range of 520 nm to 535 nm upon irradiation of anexcitation source.
 4. The phosphor according to claim 1 wherein thephosphor emits luminance derived from divalent Eu upon irradiation of anexcitation source and a half-value width of a peak of the luminance is55 nm or less.
 5. A manufacturing method of a phosphor comprising:firing a raw mixture comprising: at least metal powder including Si;metal or inorganic compound thereof including Al; metal or inorganiccompound thereof including M (here, M is Eu), in an atmospherecontaining nitrogen in a temperature range of 1200° C. or higher and2200° C. or lower.
 6. The manufacturing method of the phosphor accordingto claim 5, wherein the metal or inorganic compound thereof including Alis aluminum nitride powder, and wherein the metal or inorganic compoundthereof including M is europium oxide powder.
 7. The manufacturingmethod of the phosphor according to claim 5, further comprising: firingthe raw mixture powder in the atmosphere including nitrogen in atemperature range of 1200° C. or higher and 1550° C. or lower such thatnitrogen content of the raw mixture is increased; and then, firing theraw mixture powder at a temperature of 2200° C. or less.
 8. Amanufacturing method of a phosphor comprising: an oxygen contentreduction step of reducing oxygen content and increasing nitrogencontent in oxynitride phosphor powder having a β-type Si₃N₄ crystalstructure including Eu by heat-treating the powder in areduction-nitridation atmosphere.
 9. A manufacturing method of aphosphor comprising: heat-treating silicon nitride raw powder in areduction-nitridation atmosphere; adding raw powder containing at leastEu and Al to the treated powder in which oxygen content is reducedduring the heat treatment; and firing the powder at a temperature of2200° C. or lower after the addition.
 10. The manufacturing method ofthe phosphor according to claim 8, wherein the reduction-nitridationatmosphere contains ammonia gas, or mixed gas of hydrogen and nitrogen.11. The manufacturing method of the phosphor according to claim 8,wherein the reduction-nitridation atmosphere contains hydrocarbon gas.12. The manufacturing method of the phosphor according to claim 8,wherein the reduction-nitridation atmosphere contains mixed gas ofammonia gas and methane or propane gas.
 13. A lighting devicecomprising: a light-emitting diode (LED) or a laser diode (LD) to emitlight of wavelength of 330 to 500 nm and a phosphor wherein the phosphorcomprises a phosphor recited in claim
 1. 14. An image display devicecomprising: at least an excitation source and a phosphor wherein thephosphor is a phosphor recited in claim
 1. 15. The image display deviceaccording to claim 14 comprising: any one of a liquid display panel(LCD), a fluorescent display tube (VFD), a field emission display (FED),a plasma display panel (PDP), and a cathode-ray tube (CRT).
 16. Theimage display device according to claim 15 wherein the liquid displaypanel (LCD) comprises: an LED backlight, wherein the LED backlightcomprises: the phosphor and a light-emitting diode (LED) to emit lightof wavelength of 430 to 480 nm, and wherein the phosphor furthercomprises: a red phosphor comprising CaAlSiN₃ activated by Eu.
 17. Themanufacturing method of the phosphor according to claim 8, the oxygencontent reduction step is conducted until the oxygen content in theoxynitride phosphor powder is adjusted to 0.8 mass % or less.
 18. Themanufacturing method according to claim 8, comprising: an X-raydiffraction measurement step of measuring the manufactured phosphor todetect a β-type Si₃N₄ structure by an X-ray diffraction measurement. 19.The manufacturing method of the phosphor according to claim 9, whereinthe reduction-nitridation atmosphere contains ammonia gas, or mixed gasof hydrogen and nitrogen.
 20. The manufacturing method of the phosphoraccording to claim 9, wherein the reduction-nitridation atmospherecontains hydrocarbon gas.
 21. The manufacturing method of the phosphoraccording to claim 9, wherein the reduction-nitridation atmospherecontains mixed gas of ammonia gas and methane or propane gas.